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Ion-paired chiral ligands for asymmetric palladium catalysis

Abstract

Conventional chiral ligands rely on the use of a covalently constructed, single chiral molecule embedded with coordinative functional groups. Here, we report a new strategy for the design of a chiral ligand for asymmetric transition-metal catalysis; our approach is based on the development of an achiral cationic ammonium–phosphine hybrid ligand paired with a chiral binaphtholate anion. This ion-paired chiral ligand imparts a remarkable stereocontrolling ability to its palladium complex, which catalyses a highly enantioselective allylic alkylation of α-nitrocarboxylates. By exploiting the possible combinations of the achiral onium entities with suitable coordinative functionalities and readily available chiral acids, this approach should contribute to the development of a broad range of metal-catalysed, stereoselective chemical transformations.

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Figure 1: Strategies for construction of a chiral environment around a metal catalyst.
Figure 2: ORTEP diagram of 3b.
Figure 3: Proposed catalytic cycle for enantioselective alkylation catalysed by an ion-paired chiral catalyst.
Figure 4: Derivatization of alkylation product 6a.

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Acknowledgements

Financial support was provided by the Funding Program for Next Generation World-Leading Researchers from JSPS (GR050) and the Global COE Program in Chemistry of Nagoya University.

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Contributions

K.O. and T.O. conceived and designed the study, and co-wrote the paper. K.O., M.I. and T.K. performed the experiments and analysed the data. All authors discussed the results and commented on the manuscript.

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Correspondence to Takashi Ooi.

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The authors declare no competing financial interests.

Supplementary information

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Supplementary information

Crystallographic data for compound 3b. (CIF 23 kb)

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Ohmatsu, K., Ito, M., Kunieda, T. et al. Ion-paired chiral ligands for asymmetric palladium catalysis. Nature Chem 4, 473–477 (2012). https://doi.org/10.1038/nchem.1311

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